JP2002503259A - Reduction of carbonyl compounds with silane in the presence of zinc catalyst - Google Patents
Reduction of carbonyl compounds with silane in the presence of zinc catalystInfo
- Publication number
- JP2002503259A JP2002503259A JP54908099A JP54908099A JP2002503259A JP 2002503259 A JP2002503259 A JP 2002503259A JP 54908099 A JP54908099 A JP 54908099A JP 54908099 A JP54908099 A JP 54908099A JP 2002503259 A JP2002503259 A JP 2002503259A
- Authority
- JP
- Japan
- Prior art keywords
- group
- zinc
- reduction
- compound
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011701 zinc Substances 0.000 title claims abstract description 59
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 40
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 28
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 230000009467 reduction Effects 0.000 title claims description 68
- 239000003054 catalyst Substances 0.000 title claims description 32
- 150000001728 carbonyl compounds Chemical class 0.000 title claims description 12
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 38
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 150000002148 esters Chemical class 0.000 claims abstract description 24
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 21
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- 150000004678 hydrides Chemical class 0.000 claims abstract description 13
- 150000002576 ketones Chemical class 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 150000002596 lactones Chemical class 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract 2
- 238000006722 reduction reaction Methods 0.000 claims description 73
- -1 silane compound Chemical class 0.000 claims description 61
- 239000003446 ligand Substances 0.000 claims description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 150000001408 amides Chemical class 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 11
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 11
- 229960002887 deanol Drugs 0.000 claims description 11
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- 150000007942 carboxylates Chemical group 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 235000019197 fats Nutrition 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical group CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical group CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical group CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 150000002466 imines Chemical class 0.000 claims description 7
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical group CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 235000019198 oils Nutrition 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 6
- 150000001414 amino alcohols Chemical class 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 5
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 claims description 5
- UHBIKXOBLZWFKM-UHFFFAOYSA-N 8-hydroxy-2-quinolinecarboxylic acid Chemical compound C1=CC=C(O)C2=NC(C(=O)O)=CC=C21 UHBIKXOBLZWFKM-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 claims description 5
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 claims description 5
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 5
- LSKONYYRONEBKA-UHFFFAOYSA-N 2-Dodecanone Natural products CCCCCCCCCCC(C)=O LSKONYYRONEBKA-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- TYBCSQFBSWACAA-UHFFFAOYSA-N Nonan-4-one Chemical compound CCCCCC(=O)CCC TYBCSQFBSWACAA-UHFFFAOYSA-N 0.000 claims description 4
- 235000019483 Peanut oil Nutrition 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000004171 alkoxy aryl group Chemical group 0.000 claims description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 4
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 4
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 claims description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical group CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 claims description 4
- 229940119170 jojoba wax Drugs 0.000 claims description 4
- 239000000312 peanut oil Substances 0.000 claims description 4
- 150000008039 phosphoramides Chemical class 0.000 claims description 4
- PSQYTAPXSHCGMF-BQYQJAHWSA-N β-ionone Chemical compound CC(=O)\C=C\C1=C(C)CCCC1(C)C PSQYTAPXSHCGMF-BQYQJAHWSA-N 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 claims description 3
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000944 linseed oil Substances 0.000 claims description 3
- 235000021388 linseed oil Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 3
- SFEOKXHPFMOVRM-UHFFFAOYSA-N (+)-(S)-gamma-ionone Natural products CC(=O)C=CC1C(=C)CCCC1(C)C SFEOKXHPFMOVRM-UHFFFAOYSA-N 0.000 claims description 2
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 claims description 2
- WSWCOQWTEOXDQX-MQQKCMAXSA-M (E,E)-sorbate Chemical compound C\C=C\C=C\C([O-])=O WSWCOQWTEOXDQX-MQQKCMAXSA-M 0.000 claims description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 2
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 claims description 2
- BLKPFVWYBFDTPX-UHFFFAOYSA-N 2-(6,6-dimethyl-4-bicyclo[3.1.1]hept-3-enyl)acetaldehyde Chemical compound C1C2C(C)(C)C1CC=C2CC=O BLKPFVWYBFDTPX-UHFFFAOYSA-N 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical group CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005973 Carvone Substances 0.000 claims description 2
- 241000723346 Cinnamomum camphora Species 0.000 claims description 2
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 241000287828 Gallus gallus Species 0.000 claims description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 2
- 240000008607 Opuntia megacantha Species 0.000 claims description 2
- 235000002840 Opuntia megacantha Nutrition 0.000 claims description 2
- 235000006538 Opuntia tuna Nutrition 0.000 claims description 2
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 241001494479 Pecora Species 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- BAECOWNUKCLBPZ-HIUWNOOHSA-N Triolein Natural products O([C@H](OCC(=O)CCCCCCC/C=C\CCCCCCCC)COC(=O)CCCCCCC/C=C\CCCCCCCC)C(=O)CCCCCCC/C=C\CCCCCCCC BAECOWNUKCLBPZ-HIUWNOOHSA-N 0.000 claims description 2
- PHYFQTYBJUILEZ-UHFFFAOYSA-N Trioleoylglycerol Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(OC(=O)CCCCCCCC=CCCCCCCCC)COC(=O)CCCCCCCC=CCCCCCCCC PHYFQTYBJUILEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229960000846 camphor Drugs 0.000 claims description 2
- 229930008380 camphor Natural products 0.000 claims description 2
- 229940114081 cinnamate Drugs 0.000 claims description 2
- 229940117916 cinnamic aldehyde Drugs 0.000 claims description 2
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940043350 citral Drugs 0.000 claims description 2
- 235000019868 cocoa butter Nutrition 0.000 claims description 2
- 229940110456 cocoa butter Drugs 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002194 fatty esters Chemical class 0.000 claims description 2
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 claims description 2
- HNZUNIKWNYHEJJ-FMIVXFBMSA-N geranyl acetone Chemical compound CC(C)=CCC\C(C)=C\CCC(C)=O HNZUNIKWNYHEJJ-FMIVXFBMSA-N 0.000 claims description 2
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008169 grapeseed oil Substances 0.000 claims description 2
- 239000004571 lime Substances 0.000 claims description 2
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000003346 palm kernel oil Substances 0.000 claims description 2
- 235000019865 palm kernel oil Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 230000002207 retinal effect Effects 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 2
- 229960001860 salicylate Drugs 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229940075554 sorbate Drugs 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 claims description 2
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 claims description 2
- 229940117972 triolein Drugs 0.000 claims description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 2
- 235000012141 vanillin Nutrition 0.000 claims description 2
- 235000019871 vegetable fat Nutrition 0.000 claims description 2
- 239000010698 whale oil Substances 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 4
- 125000005609 naphthenate group Chemical group 0.000 claims 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 4
- 235000019737 Animal fat Nutrition 0.000 claims 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 3
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 claims 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims 2
- 239000004472 Lysine Substances 0.000 claims 2
- 239000003245 coal Substances 0.000 claims 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims 2
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Natural products O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 claims 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 claims 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 claims 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims 2
- 239000008158 vegetable oil Substances 0.000 claims 2
- XOLMHMBQANBLAK-UHFFFAOYSA-N 3,3-dimethyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pent-4-en-2-one Chemical compound CC(=O)C(C)(C)C=CC1CC=C(C)C1(C)C XOLMHMBQANBLAK-UHFFFAOYSA-N 0.000 claims 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical group CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims 1
- 241000283690 Bos taurus Species 0.000 claims 1
- SRBFZHDQGSBBOR-HWQSCIPKSA-N L-arabinopyranose Chemical compound O[C@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-HWQSCIPKSA-N 0.000 claims 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims 1
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- 150000001354 dialkyl silanes Chemical class 0.000 description 1
- NTMDBTSKNAXHGK-UHFFFAOYSA-N diethylaminomethanol Chemical compound CCN(CC)CO NTMDBTSKNAXHGK-UHFFFAOYSA-N 0.000 description 1
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- MKRVHLWAVKJBFN-UHFFFAOYSA-N diphenylzinc Chemical compound C=1C=CC=CC=1[Zn]C1=CC=CC=C1 MKRVHLWAVKJBFN-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
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- IMKJGXCIJJXALX-UHFFFAOYSA-N ent-Norambreinolide Natural products C1CC2C(C)(C)CCCC2(C)C2C1(C)OC(=O)C2 IMKJGXCIJJXALX-UHFFFAOYSA-N 0.000 description 1
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
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- ACJQRYKUUGFHPV-UHFFFAOYSA-N icos-1-en-1-ol Chemical compound CCCCCCCCCCCCCCCCCCC=CO ACJQRYKUUGFHPV-UHFFFAOYSA-N 0.000 description 1
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- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Chemical class 0.000 description 1
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- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- HVOYZOQVDYHUPF-UHFFFAOYSA-N n,n',n'-trimethylethane-1,2-diamine Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 description 1
- DMQSHEKGGUOYJS-UHFFFAOYSA-N n,n,n',n'-tetramethylpropane-1,3-diamine Chemical compound CN(C)CCCN(C)C DMQSHEKGGUOYJS-UHFFFAOYSA-N 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- IYRGXJIJGHOCFS-UHFFFAOYSA-N neocuproine Chemical compound C1=C(C)N=C2C3=NC(C)=CC=C3C=CC2=C1 IYRGXJIJGHOCFS-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- ILVXOBCQQYKLDS-UHFFFAOYSA-N pyridine N-oxide Chemical compound [O-][N+]1=CC=CC=C1 ILVXOBCQQYKLDS-UHFFFAOYSA-N 0.000 description 1
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- 239000012429 reaction media Substances 0.000 description 1
- NCYCYZXNIZJOKI-OVSJKPMPSA-N retinal group Chemical group C\C(=C/C=O)\C=C\C=C(\C=C\C1=C(CCCC1(C)C)C)/C NCYCYZXNIZJOKI-OVSJKPMPSA-N 0.000 description 1
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- 125000003198 secondary alcohol group Chemical group 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- SLRCCWJSBJZJBV-AJNGGQMLSA-N sparteine Chemical compound C1N2CCCC[C@H]2[C@@H]2CN3CCCC[C@H]3[C@H]1C2 SLRCCWJSBJZJBV-AJNGGQMLSA-N 0.000 description 1
- 229960001945 sparteine Drugs 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HVZJRWJGKQPSFL-UHFFFAOYSA-N tert-Amyl methyl ether Chemical compound CCC(C)(C)OC HVZJRWJGKQPSFL-UHFFFAOYSA-N 0.000 description 1
- 125000001650 tertiary alcohol group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- UARDWXPTHFQYJK-UHFFFAOYSA-K trichlorotitanium(1+) Chemical compound Cl[Ti+](Cl)Cl UARDWXPTHFQYJK-UHFFFAOYSA-K 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- 229940075466 undecylenate Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- NCYCYZXNIZJOKI-UHFFFAOYSA-N vitamin A aldehyde Natural products O=CC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C NCYCYZXNIZJOKI-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- FPROHICWJVDTNP-UHFFFAOYSA-L zinc;2-ethylbutanoate Chemical compound [Zn+2].CCC(CC)C([O-])=O.CCC(CC)C([O-])=O FPROHICWJVDTNP-UHFFFAOYSA-L 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
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- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/08—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by hydroxy groups
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
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Abstract
(57)【要約】 本発明の課題は、アルデヒド、ケトン、エステルまたはラクトンのクラスに属する基質のカルボニル基を還元して、アルコールを合成する方法であり、この場合、基質はカルボニル基以外の不飽和基を含有していてよく、ここでa)単量体であって水素化物でない、活性亜鉛化合物の触媒量の存在下に、該カルボニル基質を有効量のシラン、有利にPMHS、と反応させてシロキサンを形成し、b)このようにして得たシロキサンを塩基性剤で加水分解してアルコールにし、c)必要であれば、得られたアルコールを分離精製することから成る。この触媒活性を有する化合物は、通常、オリゴマーまたはポリマーの亜鉛前駆化合物と錯化剤との反応により獲得される。 (57) [Summary] An object of the present invention is a method for synthesizing an alcohol by reducing a carbonyl group of a substrate belonging to the aldehyde, ketone, ester or lactone class, in which case the substrate contains an unsaturated group other than the carbonyl group. Wherein a) reacting the carbonyl substrate with an effective amount of a silane, preferably PMHS, in the presence of a catalytic amount of an active zinc compound, which is a monomer and not a hydride, to form a siloxane; b) hydrolyzing the siloxane thus obtained with a basic agent to form an alcohol, and c) separating and purifying the obtained alcohol, if necessary. The compound having this catalytic activity is usually obtained by reacting a zinc precursor compound of an oligomer or a polymer with a complexing agent.
Description
【発明の詳細な説明】 亜鉛触媒存在下でのシランによるカルボニル化合物の還元 発明の属する技術分野および従来の技術 本発明は有機合成分野に関する。さらに詳細に、本発明は、アミン、ポリアミ ン、アミノアルコール、アミンオキシド、アミド、ホスホルアミド等のような塩 基性リガンドで錯化した、亜鉛単量体化合物を含有する触媒の存在下に、還元剤 としてシラン、有利にポリメチルヒドロシロキサン(PMHS)を使用してアル デヒド、ケトン、エステルおよびラクトンのようなカルボニル化合物を対応する アルコールヘ選択的に還元する方法に関する。 その間にC=O基の反応のみが観察される、カルボニル化合物の対応するアル コールへの選択的な還元は、有機化学分野において重要である。これまでは、も っぱら、水素化リチウムアルミニウムLiAlH4、水素化ホウ素ナトリウムN aBH4、または式NaAlH2(OCH2CH2OCH3)2で示される、ナトリウム ジヒドロキシビス(2−メトキシエトキシ)アルミネート(SDMA)のような 水素化物の還元剤が使用されてきたが、後者の2つの試薬は、エステルおよびラ クトンの還元に対する効果に限りがある。上記の試薬は 全て理論量で使用され、反応中または水分と接触する際の水素の解離、爆発の危 険性および使用反応器の不活性化の必要などの欠点を有する。さらに、これらの 還元剤の使用は、理論量が必要なので費用がかかる。そこで、より経済的で利用 しやすい他のシステムがなお継続的に模索されている。 いくつかの文献には、金属触媒と共にカルボニル化合物の還元剤としてシラン を使用することが記載されている。この種の還元反応に有利なシランはポリメチ ルヒドロシロキサンすなわちPMHSであり、式: で表される。 米国特許第3061424号において、NitzscheおよびWickはP MHSおよび水銀、鉄、銅、チタン、ニッケル、ジルコニウム、アルミニウム、 亜鉛、鉛、カドミウムの塩、または有利な実施態様として錫塩を使用したアルデ ヒドおよびケトンの還元について記載している。この還元システムには、プロト ン供与体による活性化が必要で、それなしにこの反応は進行しない。しかし、こ のシステムはエステルおよびラクトンの還元には効果的でない。 米国特許第5220020号において、Buchwald等は、シランの還元 剤および式M(L)(LI)(LII)からM(L)(LI)(LII)(LIII)(LVI)(LV)で示される金属 触 媒から成るシステムを利用した、カルボニル化合物の還元によるアルコールの合 成方法を記載しており、ここでMは周期表の3、4、5または6族のいずれかに 属する金属、ランタノイドまたはアクチノイドであり、(LI)から(LV)は水素、ア ルキル基、アリール基、シリル基、ハロゲン原子、または−OR、−SRまたは −NR(R')基であり、RおよびR'は水素、アルキルまたはアリール基である 。引用した特許では、有利な触媒の中に、チタン(IV)イソプロピレート、チ タン(IV)エチレートまたはトリクロロチタン(IV)イソプロピレートにつ いての記載がある。このシステムはエステル、ラクトン、アミドまたはイミンの 還元に適すると述べられている。さらに最近では、BreedonとLawre nce(Synlett.,1994,833)およびRedingとBuchwald(J.Org.Che m.,1995,60,7884)が同様の方法、すなわちPMHSでエステルを還元するための 触媒として非活性化チタンテトラアルコキシドを使用することを記載している。 前記3つの引用文献に記載された方法では、基質あたり少なくとも25モル%と いう大量の触媒の使用が必要である。Barr、BerkおよびBuchwal d(J.Org.Chem.,1994,59,4323)は、臭化ブチルリチウムまたは臭化エチルマグネ シウムによる還元時に、錯体CP2TiCl2が触媒して高い収量でエステルを対 応するアルコールへ還元することを示しているが、 この技術には高価な試薬が必要であり、また工業的有機合成のような大規模な使 用は困難である。 最新技術として国際出願特許WO96/12694を引用すべきで、ここには 、シランおよび金属水素化物から成る還元システムにより、高い収率で対応する アルコールに導く、アルデヒド、ケトン、エステルおよびラクトンの還元につい ての記載がある。このシステムには、基質あたり1モル%程度の非常に少量の触 媒、すなわち金属水素化物、しか必要ない。この水素化物は各金属塩と適当な還 元剤、有利にNaBH4、との反応により合成される。亜鉛塩の他にも、コバル ト、マンガン、鉄の塩を金属水素化物を製造するための前駆物質として使用する 。有利な実施態様においては、シラン還元剤としてPMHSを使用する。 発明の詳細な説明 水素化物でなく、そのためにNaBH4のような還元剤の使用を必要としない 金属誘導体で触媒される、シランを用いたカルボニル化合物の還元方法の開発に 成功した。 本発明の課題は、アルデヒド、ケトン、エステルまたはラクトンのクラスに属 する基質のカルボニル基を還元して、アルコールを合成する方法であり、この場 合、基質はカルボニル基以外の不飽和基を含有していてよく、ここで a)単量体であって水素化物でない、活性亜鉛化合 物の触媒量の存在下に、該カルボニル基質を有効量のシラン、有利にPMHS、 と反応させてシロキサンを形成し、 b)このようにして得たシロキサンを塩基性剤で加水分解してアルコールにし 、 c)必要であれば、得られたアルコールを分離精製する。 本発明の別の課題は、 a)シラン、有利にPMHS、および b)単量体であって水素化物でない活性亜鉛化合物から成る還元システムであ る。 本発明は、単量体型の亜鉛の使用が、シランおよび亜鉛化合物から成るカルボ ニル化合物のための還元システムの反応性を、強力に高めるという意外な事実に 基づいている。すなわち、先に引用したNitzscheおよびWickによる 米国特許第3061424号に記載されたような亜鉛塩およびシランを含む還元 システムは、本明細書のシステムと比べてはるかに低反応性である。特に、従来 の技術において記載した還元システムでは、本発明の還元システムと異なり、エ ステルおよびラクトンを還元できない。 他方、先に引用したWO96/12694の明細書では、亜鉛の塩または錯体 の添加によりカルボニル基質の還元に用いるシランの反応性が強化される可能性 を示しているものの、亜鉛の塩または錯体は還元剤に よる活性化を要する。還元剤として、NaBH4、LiAlH4、リチウムアルキ ル、アルミニウムアルキル、グリニャール化合物のような化合物を、高反応性種 、すなわち水素化物、の生成のために使用している。 しかし本発明では、還元剤による活性化を必要とせず、理論量をシランといっ しょに使用する時、あらゆる種類のカルボニル化合物の還元を触媒できるような 亜鉛化合物、例えば亜鉛塩または亜鉛錯体、を用いる。 亜鉛の化学的性質は、原子価状態が+2の結果である、配位数2よりも大きく なる傾向の金属として一般的に特徴づけられ、そのため亜鉛は、達成することが 望まれる高い配位数をオリゴマー化および重合により獲得することもでき、その 場合は一般的に4配位、または6配位となる。この理由のために、亜鉛塩または 亜鉛錯体は、たいていオリゴマーまたはポリマーであり、例としてここでは亜鉛 カルボキシレートおよび亜鉛ハロゲン化物を挙げる。 しかし、電子的に不飽和な化合物クラスには、ジアルキル亜鉛化合物およびジ アリール亜鉛化合物もある。これらは、アルキルおよびアリール基が架橋リガン ドとして働くことができないために、オリゴマー化または重合によって配位数を 2より大きくできない。それ故、ジアルキル亜鉛化合物およびジアリール亜鉛化 合物は単量体で存在し、直鎖構造となる。 カルボニル化合物を還元するために使用した場合、前記化合物の全てが、全く 活性を示さないか、または非常に低活性であるかのどちらかであることを見出し た。しかし、ジアルキル亜鉛化合物またはジアリール亜鉛化合物と同様、ポリマ ーまたはオリゴマー型亜鉛化合物を、単量体活性種を生成する能力のある適当な 錯化剤で処理すると、シランによるアルデヒド、ケトン、エステルおよびラクト ンの還元に対して非常に効果的な触媒となる。 本発明により、オリゴマーまたはポリマーの前駆化合物、またはジアルキル亜 鉛化合物やジアリール亜鉛化合物を、適当な錯化剤で処理して活性の塩または錯 体に変換して使用できる。さらに、本発明の方法により活性体に変換される公知 の単量体の錯体または塩も使用できることを見出したが、その活性に関してはこ れまで全く知られていなかった。 前駆化合物として、実際には、一般式ZnX2で示される公知の亜鉛化合物を 使用できる。式中Xは、任意の陰イオンを意味する。有利な陰イオンXを以下に 示す。 本発明の活性な触媒を一般式ZnX2Lnで表わすことができる。触媒は、前記 の一般式ZnX2で示される塩または錯体のような亜鉛化合物から、反応媒質中 でその場で獲得でき、別に合成できる。一般式ZnX2で示される前駆化合物お よびZnX2Lnで示される 活性触媒中のXは、有利にカルボキシレート、β−ジケトネート、エノレート、 アミド、シリルアミド、ハライド、カーボネートおよびシアニド、およびアルキ ル、シクロアルキル、アルコキシ、アリール、アリールオキシ、アルコキシアル キル、アルコキシアリール、アラルコキシ、アラルコイルおよびアルキルアリー ル基のような有機基から成る群より選択される陰イオンである。この群の中でも 、例えばアセテート、プロピオネート、ブチレート、イソブチレート、イソバレ レート、ジエチルアセテート、ベンゾエート、2−エチルヘキサノエート、ステ アレートまたはナフトエートのような式Zn(RCO2)2で示される亜鉛カルボ キシレート;メトキシド、エトキシド、イソプロポキシド、tert−ブトキシド、 tert−ペントキシド、または8−ヒドロキシキノリネートのような式Zn(OR )2で示される亜鉛アルコキシド(ここでRはC1〜C20、有利にC1〜C5のアル キル基である);置換のまたは非置換のアセチルアセトネート、トロポロネート のような亜鉛β−ジケトネート;炭素原子を1〜20、有利に1〜5個を有する アルキル亜鉛化合物、アリール亜鉛化合物、アルキル(アルコキシ)亜鉛化合物 、アリール(アルコキシ)亜鉛化合物またはこれらの誘導体、たとえばジメチル 亜鉛、ジエチル亜鉛、ジプロピル亜鉛、ジブチル亜鉛、ジフェニル亜鉛、メチル (メトキシ)またはメチル(フェノキシ)亜鉛、または ハロゲン化(アルキル)亜鉛の誘導体、を有利に使用する。 式ZnX2Ln中のnは1〜6の整数である。リガンドLは、同一でも異なって いてもよく、アミン、ポリアミン、イミン、ポリイミン、アミノアルコール、ア ミンオキシド、ホスホルアミドおよびアミドから成る群より選択される。 このアミンは一級、二級または三級の、炭素原子を2〜30個有する脂肪族、 脂環式、または芳香族アミンである。例としては、アニリン、トリエチルアミン 、トリブチルアミン、N,N−ジメチルアニリン、モルホリン、ピペリジン、ピ リジン、ピコリン、ルチジン、4−テルチオブチルピリジン、ジメチルアミノピ リジン、キノリンおよびN−メチルモルホリンがあるが、この例に限定するもの ではない。 ポリアミンは2〜6個の一級、二級または三級アミン基を有し、炭素原子2〜 30個から成り、例えばエチレンジアミン、1,2−プロピレンジアミン、1,3 −プロピレンジアミン、1,2−ブタンジアミン、1,3−ブタンジアミン、1, 4−ブタンジアミン、ヘキサメチレンジアミン、N,N−ジメチルエチレンジア ミン、ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミ ン、テトラメチルエチレンジアミン、N,N−ジメチルプロピレンジアミン、N, N,N'−トリメチルエチレンジアミン、N,N,N',N'− テトラメチル−1,3−プロパンジアミン、ヘキサメチレンテトラミン、ジアザ ビシクロノナン、スパルテイン、オルトフェナントロリン、2,2'−ビピリジン およびネオクプロインがある。 アミノアルコールは、ひとつまたは幾つかの一級、二級または三級アルコール 基といっしょになった、ひとつまたは幾つかの一級、二級または三級アミン基か ら成り、例えば、エタノールアミン、ジエタノールアミン、トリエタノールアミ ン、ジメチルアミノエタノール、ジエチルアミノエタノール、ジメチルアミノメ タノール、ジエチルアミノメタノール、2−アミノブタノール、エフェドリン、 プロリノール、バリノール、シンコニジン、キニンおよびキニジンがある。 本発明の概念において、イミンまたはジイミンのファミリーに属し、亜鉛誘導 体または亜鉛化合物を活性化するリガンドとして、下記の式[I]から[V]の 化合物ファミリー(ここで、各基R1からR6は水素原子または炭素原子を1〜2 0個有するアルキル、シクロアルキル、アルコキシ、アリール、アリールオキシ 、アルコキシアルキル、アルコキシアリール、アラルコキシ、アラルコイル、ア ルキルアリールまたはアラルキル基である)があるが、この例に限定するもので はない。 亜鉛化合物および亜鉛誘導体を活性化できるその他のリガンドはなおもアミド を含み、例えば、ジメチルホルムアミド、ジメチルアセタミドまたはN−メチル −ピロリドン、ヘキサメチルホスホルトリアミドのようなホスホルアミド、トリ フェニルホスフィンオキシド、トリブチルホスフィンオキシド、トリオクチルホ スフィンオキシドのようなホスフィンオキシド、ピリジンN−オキシド、4−ピ コリン−N−オキシド、N−メチル−モルホリンN−オキシドのようなアミンオ キシド、ジメチルスルホキシドまたはジフェニルスルホキシドのようなスルホキ シドがある。 本発明は、本発明の方法により活性体となる亜鉛錯体の単量体にも関する。化 合物の有利なクラスは、亜鉛カルボキシレートの単量体である。Zn(O2CC H3)2(ピリジン)2(J.Am.Chem.Soc.119,7030(1997)参照)以外のこの分子 クラスは、化学文献中に記載がない。 これらの錯体の中で有利な化合物として、ここに挙げる[Zn(ベンゾエート )2(Me2NCH2CH2OH)2]、[Zn(ジエチルアセテート)2(2,2'−ビ ピリジル)]、[Zn(ジエチルアセテート)2(1,2−ジア ミノプロパン)2]および[Zn(ベンゾエート)2(TMEDA)](TMEDA=テト ラメチルエチレンジアミン)がある。これらの化合物の合成および特性を以下に 記載する。 本発明の方法では、多数のシランを使用することができる。そのようなシラン は当業者に公知であり、本発明の方法におけるカルボニル基質を効果的に還元す る能力に応じて選択できる。例としてトリアルキルシラン、ジアルキルシランま たはトリアルコキシシランがあるが、この例に限定するものではない。さらに特 殊な例として、ジメチルシラン、ジエチルシラン、トリメトキシシランおよびト リエトキシシランがある。効果、有用性、費用の而から考えてPMHSを使用す るのが有利である。 還元剤としてPMHSを使用した有利な場合を例にあげて、本発明の方法を以 下のスキームにより概要する。 基質あたりのモル%で示した触媒ZnX2Lnの濃度は、通常0.1〜10モル %、有利に1〜5モル%である。 PMHSは通常、エステルまたはラクトン基あたり2モル当量、アルデヒドお よびケトンの還元に1当量が消費される。実際には、理論量をわずかに上回るP MHSを使用することが有利であり、通常理論量の10〜40%過剰程度で使用 する。シランを準−理論量で使用する場合にも本発明の還元反応を実施できるが 、結果として変換量が減少する。すなわち本発明において“有効量”とは、シラ ンの量が基質の還元を誘導するのに十分であることを意味する。 反応生成物として得られるアルコールは、形成したポリシリルエーテルの加水 分解で獲得できる。この加水分解は、たとえば水酸化ナトリウム、水酸化カリウ ム、石灰、炭酸ナトリウム、炭酸カリウムのような塩基性剤の水溶液またはアル コール溶液を反応混合物に添加することで実施できる。使用するPMHSに対す る塩基の割合は、約1〜2モル当量である。完全に加水分解した後、一般的に2 相の形成が観察される。所望のアルコールは有機相にあり、存在する溶媒を蒸発 させて獲得できる。得られた残留物をさらに精製するために蒸留してもよい。 この還元は溶媒がなくてもあっても実施でき、溶媒にはたとえばエーテル(例 えばメチルtert−ブチルエ ーテル、ジイソプロピルエーテル、ジブチルエーテル、tert−アミルメチルエー テル、テトラヒドロフランまたはジオキサン)、脂肪族炭化水素(例えばヘプタ ン、石油エーテル、オクタン、またはシクロヘキサン)または芳香族炭化水素( 例えばベンゼン、トルエン、キシレンまたはメシチレン)またはそれらの混合物 がある。 前記のように、本発明の還元は、オレフィン、アセチレン、ニトリルまたはニ トロ基のような、還元反応の影響を受けないカルボニル基以外の不飽和基を含有 する様々なカルボニル化合物に適用できる。 アルデヒド基質の例として、直鎖または分枝鎖のブタナール、ペンタナール、 ヘプタナール、オクタナール、デカナール、ドデカナールがあるが、この例に限 定するものではない。選択的に還元されて対応する不飽和アルコールとなる、そ の他の不飽和アルデヒドには、アクロレイン、メタクロレイン、プレナール、シ トラール、レチナール、カンホレンアルデヒド(campholene aldehyde)、ケイ皮 アルデヒド、ヘキシルケイ皮アルデヒド、ホルミルピナンおよびノパールが含ま れる。ベンズアルデヒド、クミンアルデヒド、バニリン、サリシルアルデヒドま たはヘリオトロピンのような芳香族アルデヒドも容易に対応するアルコールへと 還元される。 本発明のようにして、シランにより対応するアルコ ールへと還元される飽和および不飽和ケトンには、ヘキサン−2−オン、オクタ ン−2−オン、ノナン−4−オン、ドデカン−2−オン、メチルビニルケトン、 メシチルオキシド、アセトフェノン、シクロペンタノン、シクロデカノン、シク ロヘキセン−1−エン−3−オン、イソホロン、オキソホロン、カルボン、カン ファー、β−イオノン、ゲラニルアセトンおよび2−ペンチルシクロペンテン− 2−オンがあるが、これらの例に限定するものではない。 本発明のようにして、シランにより対応するアルコールへと還元される飽和お よび不飽和のエステルまたはラクトンには、アセテート、プロピオネート、ブチ レート、イソブチレート、ベンゾエート、アクリレート、クロトネート、シンナ メート、シス−3−ヘキセノエート、ソルベート、サリシレート、10−ウンデ シレネート、オレエート、リノレエート、天然脂肪酸のエステルおよびこれらの 混合物があるが、この例に限定するものではない。この他の例にはε−カプロラ クトン、デカラクトン、ドデカラクトン、ジケテンおよびスクラレオリドのよう なラクトンを含むが、この例に限定するものではない。 本発明の触媒の特記すべき特徴は、植物性油脂および動物性油脂を形成するよ うな脂肪酸の天然トリグリセリドの還元が可能なことである。異なる脂肪酸由来 トリグリセリド混合物の反応過程で、オレフィン様二 重結合の位置および立体化学構造を変化させることなく、飽和および不飽和天然 アルコールを同時に獲得できる。このことは、シス配置のオレフィン結合におい て特に有意である。 上記のスキーム(3)において、置換基R1、R2およびR3は炭素原子を1〜 20個有する炭化水素基であり、同一でも異なっていてもよい。これらの基が特 定の立体化学的オレフイン基(一般的にはシス体)をひとつまたはそれ以上含む 場合、本発明の還元後に得られる対応のアルコールも同じ立体化学構造を有する 。従って、あまに油のようにリノール酸および/またはリノレン酸を多く含む油 脂は、リノレイルアルコールおよび/またはリノレニルアルコールを多く含む混 合物へと変換される。植物性油脂を水素化する慣用の方法は、本発明とは対照的 に、通常、高圧高温で実施する。さらに、このような慣用の水素化では、メタノ ールで油脂をトランスエステル化して得た、各酸のメチルエステルを用いるので 、多くの場合、トランスエステル化および水素化反応の過程で、脂肪エステル前 駆物質の立体化学構造の変化が認められる。 本発明の方法で還元されたトリグリセリドには、トリオレイン、ピーナッツオ イル、大豆油、オリーブオ イル、なたね油、ゴマ油、ぶどう種油、あまに油、カカオバター、パーム油、パ ーム核油、コットンオイル、コプラ油、ココナッツオイル、および豚、牛、羊お よび鶏の脂肪があるが、この例に限定するものではない。 天然に存在し、トリグリセリドではないが不飽和脂肪酸と一価の不飽和アルコ ールとのエステルであるその他の油脂には、ホホバオイルおよび鯨油があり、エ ステル分子中に存在する二重結合の位置および立体化学構造を変化させることな く、本発明の方法で還元できる。 反応温度は広い範囲の値で変化させることができ、通常−50〜250℃の範 囲である。選択された温度は基質の反応性に依存し、難なく適切に調整できる。 より一般的には、反応を50〜110℃の温度範囲で実施する。 次の実施例で本発明をより詳細に説明する。実施例において、温度は摂氏であ り、収量はモル%であり、NMRデータの化学シフトδは内部標準であるテトラ メチルシランに対するppmであり、これらの省略形は当業者に公知である。 実施例 例1 錯体[Zn(ベンゾエート)2(Me2NCH2CH2OH)2]の合成 この化合物を以下の記載およびスキーム(4)の例図に従って合成した。 ジクロロメタン50ml中の亜鉛ベンゾエート3.06g(10ミリモル)懸 濁液に、ジメチルアミノエタノール1.8g(20ミリモル)を添加した発熱反 応が観察され、亜鉛ベンゾエートは完全に溶解した。20℃で1時間撹拌した後 に溶媒を蒸発させ、得られた固体残留物を最少量のジクロロメタンから結晶化し た。所望の錯体3.9g(80%)を白色の固体結晶として獲得し、その構造を 単一結晶からX線構造解析により確認した。 例2 錯体[Zn(ジエチルアセテート)2(2,2'−ビピリジル)]の合成 この化合物を、スキーム(5)に従い、下記のようにして合成した。 亜鉛ジエチルアセテート3g(10ミリモル)をジイソプロピルエーテル50 ml中に溶解した。その後リガンド2,2'−ビピリジル10ミリモルを添加し、 次いで混合物を20℃で撹拌した。速やかに沈殿物を生じ、これを濾過により分 離し、シクロヘキサンから再結晶化した。収量は80%であった。例3 錯体[Zn(ベンゾエート)2(テトラメチルエチレンジアミン)]の合成 この化合物を以下の記載およびスキーム(6)の概要に従って合成した。 この反応を、ジメチルアミノエタノール2当量の代わりにテトラメチルエチレ ンジアミン1当量を使用し、実施例1の記載と同様に実施した。収量:85%。 例4 錯体[Zn(ジエチルアセテート)2(1,2−ジアミノプロパン)2]の合成。 この化合物を、スキーム(7)に従い、下記のようにして合成した。 この反応を、2,2'−ビピリジル1当量の代わりに1,2−ジアミノプロパン 2当量を使用して、実施例2の記載と同様に実施した。収量=75%。還元反応 例5 250mlの三つ首フラスコ中に、イソプロピルエーテル30gおよびメチル ベンゾエート27.2g(0.2モル)を、次いで例2で合成した結晶性錯体、す なわち[Zn(ジエチルアセテート)2(2,2'−ビピリジル)]4ミリモルを入 れた。混合物を15分かけて70℃まで加熱(還流)し、PMHS30g(0. 44モル)を添加した。この混合物を、基質が完全に消失するまで(GC分析に より測定)、さらに1時間還流下に撹拌した。混合物を20℃まで冷却し、迅速 に撹拌しながらKOHの45%水溶液66g(0.52モル)をし、その後さら に1時間撹拌した。次いで、水100gを添加し、混合物をデカントした。カリ ウムポリメチルシリコネートを含有する水相をデカントし、有機相を水50ml で洗浄した。溶媒を蒸留により除去し、粗生成物21gを得た。残留物からの蒸 留では、ベンジルアルコール20.5gが純度98%以上で得られた(収量=9 5%)。 例6(比較例) この反応を、触媒としてポリマーの亜鉛ジエチルアセテート1.12g(4ミ リモル)を使用したことを除いて、実施例5と同様に実施した。4時間後にも使 用したメチルベンゾエートの反応は観察されず、このことは、適切なリガンドの 存在が解重合反応に必須であること、したがってエステル還元に要する亜鉛のジ エ チルアセテートの活性化に必須であることを示している。 例7〜23 表1にまとめたこれらの実施例は、PMHSによるメチルベンゾエートのベン ジルアルコールへの還元において、二座リガンドの添加が亜鉛カルボキシレート の触媒活性に及ぼす重要な影響について示している。反応条件を表の下に記載し たが、これらは例5と類似している。この表から、単離錯体のカルボキシレート 基が有する赤外バンドυ(CO2)asおよびυ(CO2)sの位置も分かり、これ により、触媒活性を獲得する前から亜鉛カルボキシレート前駆物質の解重合を確 認できる。 表1 メチルベンゾエートのベンジルアルコールへの還元。二座リガンドの性質 による影響。 例24〜30 表2にまとめたこれらの実施例は、PMHSによるメチルベンゾエートの還元 において、単座リガンドの添加が亜鉛カルボキシレートの触媒活性に及ぼす重要 な影響について示している。この反応を、基質のメチルベンゾエートおよび亜鉛 ジエチルアセテート2モル%を単座リガンド4モル%といっしょにして使用し、 前記記載と同様に実施した。 表2 単座リガンドで錯化した亜鉛カルボキシレートの存在下でのPMHSによ るメチルベンゾエートの還元。 例31〜36 これらの実施例は、PMHSを使用してエステルを還元するために用いるアセ チルアセトネートのような亜鉛β−ジケトネートの触媒活性に関して、これまで に明記したリガンドの添加が有利に影響することを示している。亜鉛アセチルア セトネートが三量体構造を有し、これが2,2'−ビピリジルのような二座リガン ドと反応すると単量体で、かつ八面体となることが公知である。 下の表3は、亜鉛アセチルアセトネートそれ自身がPMHSによるエステルの 還元において低い活性しか有さないことを示している。 亜鉛アセチルアセトネートに一級または二級ジアミン1当量を添加することに より、メチルベンゾエートを対応するアルコールへ完全に変換させる触媒作用を 有する亜鉛錯体を獲得できる。 表3 様々なリガンドで錯化した亜鉛アセチルアセトネートの存在下における、 PMHSによるメチルベンゾエートの還元。 例37〜42 これらの実施例は、PMHSを使用してエステルを還元する場合に用いるジエ チル亜鉛のようなジアルキル亜鉛化合物の触媒活性に関して、これまでに明記し たリガンドの添加が有利に影響することを示している(表4)。ジアルキル亜鉛 化合物は単量体でC−Zn−Cの角度が180°である直鎖構造を有しており、 本発明の条件下では反応しない。三級ジアミンのような二座リガンドLの存在下 では、ZnR2Lで示される四面体構造の単量体錯体を形成する[O'Brien等、J.O rganomet.Chem.,1993,449,let1993,461,5参照]。 表4 様々なリガンドで錯化したジエチル亜鉛の存在下におけるPMHSによる メチルベンゾエートの還元。例43〜47 これらの実施例は、PMHSを使用してエステルを還元する場合に用いる亜鉛 アルコキシドの触媒活性に関して、これまでに明記したリガンドの添加が有利に 影響することを示している。表5は、無水塩化亜鉛1当量ヘカリウムtert−ペン トキシド(トルエン溶液中)2当量を添加することにより、その場で形成された 、亜鉛tert−ペントキシレートはPMHSによるメチルベンゾエートの還元に対 して顕著な活性を示さない が、一級、二級または三級ジアミンを添加すると、高活性の触媒になることを示 している。 表5 様々なリガンドで錯化した亜鉛アルコキシドの存在下におけるPMHSに よるメチルベンゾエートの還元。例48〜52 反応をジイソプロピルエーテルの還流下に、基質あたり亜鉛ジエチルアセテー ト2モル%およびジメチルアミノエタノール2モル%を含有する混合物を使用し て、実施例5記載と同様に実施した。各エステルを20ミリモル使用し、PMH S44ミリモルで還元した。基質が消失したら、KOH(KOHの45%水溶液 の形)60ミリモルを用いて加水分解した。デカンテーシヨンし、溶媒を蒸発さ せた後、生じたアルコールを蒸留した。表6に示した結果から分かるように、ど の場合にも出発化合物の立体化学構造には影響なかった。 表6 ジメチルアミノエタノールで錯化した亜鉛ジエチルアセテートの存在下に おけるPMHSによる様々なエステルの還元。例53〜59 反応をジイソプロピルエーテルの還流下に、基質あたり亜鉛ジエチルアセテー ト2モル%および表7に記載したリガンドのいずれかひとつ2モル%を含有する 混合物を使用して、実施例5記載と同様に実施した。基質として、各アルデヒド またはケトンを20ミリモル使用し、PMHS22ミリモルで還元した。基質が 完全に消失したら、KOH(KOHの45%水溶液の形)60ミリモルを用いて 加水分解した。デカンテーションし、溶媒を蒸発させた後、生じたアルコールを 蒸留した。表7の結果は、いずれの反応もアルデヒドおよびケトンの還元が出発 物質の立体化学構造を変化させることなく、良好な収量で進行したことを示して いる。 表7 様々なリガンドで錯化した亜鉛ジエチルアセテートの存在下におけるPM HSによる種々のアルデヒドおよびケトンの還元。例60〜62 この反応は、触媒としてZnF2を使用して、実施例5記載と同様に実施した 。この結果から、亜鉛ハロゲン化物がこの種の還元において活性であることが分 かった。 表8 様々なリガンドで錯化したZnF2の存在下におけるPMHSによるメチ ルベンゾエートの還元。例63 ピーナッツオイルの還元 11の三つ首フラスコに、トルエン200ml、亜鉛2−エチルヘキサノエー ト11g(0.03モル)およびジメチルアミノエタノール5.34g(0.06 モル)を入れた。次に、ピーナッツオイル200gを添加し、混合物を還流下に 加熱した(110℃)。1時間かけてPMHS200g(0.5モル)を添加し 、混合物をさらに2時間還流した。その後、KOHの30%メタノール溶液で加 水分解したサンプルをGC分析したところ、反応混合物中のアルコール量は一定 であった。次いで混合物をKOHの30%メタノール溶液450g中に注ぎ、さ らに1時間50℃に保持した。次いで水300gを添加し、混合物をデカントし た。次いで溶媒を有機相から蒸発させ、残留物を200〜250℃/1hPaで 蒸留し、1−ヘキサデカノール 14%、オレイルアルコール55%およびリノレイルアルコール17%を含む混 合物100gを得た。 例64 エチルソルベートの還元 還流コンデンサー、内部温度計、シリンジポンプおよび電磁撹拌機を備えた1 1の三つ首フラスコ中にZn(2−エチルヘキサノエート)2 13.3g(基質 あたり4モル%)、ジメチルアミノエタノール4g(4モル%)、トルエン10 mlを入れ、80℃まで加熱した。次いでエチルソルベート210.1g(1.5 モル)、BHT(2,4−ジ−tert−ブチル−p−クレゾール)0.42g、トル エン(ca200ml)を添加し、溶液を還流した。PMHS213g(2.1当 量相当)を90分かけて添加し、反応混合物をさらに30分還流して加熱した。 混合物を完全に加水分解するまでNaOHの30%水溶液630g上に注ぎ、有 機相をデカントし、水で洗浄した。粗生成物をビグロー(vigreux)タイプのカ ラム(10hPa)上で蒸留してヘキサ−2,4−ジエン−1−オール120.7 g(83.4%)を得た。 例65 ホホバオイルの還元 還流コンデンサー、内部温度計、シリンジポンプおよび電磁撹拌機を備えた2 50mlの三つ首フラスコにホホバオイル50g、Zn(2−エチルヘキサノエ ート)2 0.2g(エステル基あたり約4モル%相当)、ジメチルアミノエタノ ール0.06g(約4モル%)およびトルエン50mlを入れた。混合物を還流 して加熱し、PMHS6.5g(0.1モル、約2.2当量)を45分かけて添加 した。還流をさらに30分継続し、反応混合物をNaOHの30%水溶液50g 中に注いだ。完全に加水分解してから有機相をデカントし、水で洗浄した。この ようにして得た粗生成物をバルブーバルブ(bulb-to-bulb)装置で250°/1h Paで蒸留し、(Z)−9−オクタデカン−1−オール6.4%、(Z)−9− イコセン−1−オール59.3%、(Z)−9−ドコセン−1−オール26.8% および(Z)−9−テトラコセン−1−オール3.9%を含有する生成物48.4 g(95%)を得た。Description: TECHNICAL FIELD The present invention relates to the field of organic synthesis. More specifically, the present invention provides a method for reducing a compound as a reducing agent in the presence of a zinc monomer compound-containing catalyst complexed with a basic ligand such as an amine, polyamine, amino alcohol, amine oxide, amide, phosphoramide, and the like. It relates to a method for the selective reduction of carbonyl compounds such as aldehydes, ketones, esters and lactones to the corresponding alcohols using silanes, preferably polymethylhydrosiloxane (PMHS). The selective reduction of the carbonyl compound to the corresponding alcohol, during which only the reaction of the C = O group is observed, is important in the field of organic chemistry. Until now, lithium aluminum hydride LiAlH Four , Sodium borohydride NaBH Four Or the formula NaAlH Two (OCH Two CH Two OCH Three ) Two Although hydride reducing agents such as sodium dihydroxybis (2-methoxyethoxy) aluminate (SDMA) have been used, the latter two reagents have limited effects on the reduction of esters and lactones. is there. All of the above reagents are used in stoichiometric amounts and have disadvantages such as the dissociation of hydrogen during the reaction or on contact with moisture, the danger of explosion and the need to deactivate the reactor used. In addition, the use of these reducing agents is costly because of the theoretical amount required. Thus, other systems that are more economical and accessible are still being sought. Several documents describe the use of silanes as reducing agents for carbonyl compounds with metal catalysts. A preferred silane for this type of reduction reaction is polymethylhydrosiloxane, or PMHS, of the formula: It is represented by In U.S. Pat. No. 3,061,424, Nitzsche and Wick used PMHS and salts of mercury, iron, copper, titanium, nickel, zirconium, aluminum, zinc, lead, cadmium, or aldehydes and ketones using tin salts in a preferred embodiment. The reduction of is described. The reduction system requires activation by a proton donor without which the reaction does not proceed. However, this system is not effective for reducing esters and lactones. In U.S. Pat. No. 5,220,020, Buchwald et al. Disclose a reducing agent for silane and a formula M (L) (L I ) (L II ) To M (L) (L I ) (L II ) (L III ) (L VI ) (L V The present invention describes a method for synthesizing an alcohol by reduction of a carbonyl compound using a system comprising a metal catalyst represented by the following formula: wherein M is a metal belonging to any of Groups 3, 4, 5, or 6 of the periodic table; Lanthanoid or actinoid, (L I ) To (L V ) Is hydrogen, an alkyl group, an aryl group, a silyl group, a halogen atom, or a —OR, —SR or —NR (R ′) group, and R and R ′ are a hydrogen, an alkyl or an aryl group. The cited patents describe among the preferred catalysts titanium (IV) isopropylate, titanium (IV) ethylate or trichlorotitanium (IV) isopropylate. The system is stated to be suitable for the reduction of esters, lactones, amides or imines. More recently, Breedon and Lawrence (Synlett., 1994, 833) and Reding and Buchwald (J. Org. Chem., 1995, 60, 7844) have used similar methods, namely catalysts for reducing esters with PMHS. Describes the use of non-activated titanium tetraalkoxide. The methods described in the three references require the use of large amounts of catalyst, at least 25 mol% per substrate. Barr, Berk and Buchwald (J. Org. Chem., 1994, 59, 4323) gave the complex CP upon reduction with butyllithium bromide or ethylmagnesium bromide. Two TiCl Two Has shown that it can catalyze the reduction of esters to the corresponding alcohols in high yields, but this technique requires expensive reagents and is difficult to use on a large scale, such as in industrial organic synthesis. . The state of the art should be cited in international application WO 96/12694, which describes the reduction of aldehydes, ketones, esters and lactones in high yields to the corresponding alcohols by means of a reduction system consisting of silanes and metal hydrides. There is a description. This system requires only a very small amount of catalyst, i.e. metal hydride, of the order of 1 mol% per substrate. The hydride is prepared by combining each metal salt with a suitable reducing agent, preferably NaBH Four And is synthesized by the reaction with In addition to zinc salts, salts of cobalt, manganese and iron are used as precursors for producing metal hydrides. In a preferred embodiment, PMHS is used as the silane reducing agent. DETAILED DESCRIPTION OF THE INVENTION Not hydride, therefore NaBH Four A method for reducing a carbonyl compound using silane, which is catalyzed by a metal derivative that does not require the use of a reducing agent, was successfully developed. An object of the present invention is a method for synthesizing an alcohol by reducing a carbonyl group of a substrate belonging to the class of aldehyde, ketone, ester or lactone, wherein the substrate contains an unsaturated group other than the carbonyl group. A) reacting the carbonyl substrate with an effective amount of a silane, preferably PMHS, in the presence of a catalytic amount of an active zinc compound, which is a monomer and not a hydride, to form a siloxane; b) The siloxane thus obtained is hydrolyzed with a basic agent to form an alcohol. c) If necessary, the obtained alcohol is separated and purified. Another object of the present invention is a reduction system comprising a) a silane, preferably PMHS, and b) a monomeric, non-hydride active zinc compound. The present invention is based on the surprising fact that the use of monomeric zinc strongly enhances the reactivity of the reduction system for carbonyl compounds consisting of silanes and zinc compounds. That is, a reduction system comprising a zinc salt and silane, such as described in the previously cited U.S. Pat. No. 3,061,424 to Nitzsch and Wick, is much less reactive than the systems herein. In particular, the reduction system described in the prior art cannot reduce esters and lactones, unlike the reduction system of the present invention. On the other hand, although the specification of WO 96/12694 cited above shows that the addition of a salt or complex of zinc may enhance the reactivity of the silane used for the reduction of the carbonyl substrate, the salt or complex of zinc is Activation by a reducing agent is required. NaBH as a reducing agent Four , LiAlH Four , Lithium alkyls, aluminum alkyls, Grignard compounds have been used for the production of highly reactive species, ie hydrides. However, in the present invention, a zinc compound, such as a zinc salt or a zinc complex, which can catalyze the reduction of any kind of carbonyl compound when used in combination with a silane in a stoichiometric amount does not require activation by a reducing agent. . The chemistry of zinc is generally characterized as a metal that tends to be larger than coordination number 2, which is the result of a valence state of +2, so that zinc has a high coordination number that it is desired to achieve. Can also be obtained by oligomerization and polymerization, in which case it will generally be four-coordinate or six-coordinate. For this reason, zinc salts or zinc complexes are mostly oligomers or polymers, examples here being zinc carboxylate and zinc halide. However, the class of electronically unsaturated compounds also includes dialkyl zinc compounds and diaryl zinc compounds. They cannot have a coordination number greater than 2 by oligomerization or polymerization because the alkyl and aryl groups cannot serve as bridging ligands. Therefore, the dialkyl zinc compound and the diaryl zinc compound exist as monomers and have a linear structure. When used to reduce carbonyl compounds, all of the compounds were found to show either no activity or very low activity. However, similarly to dialkyl or diaryl zinc compounds, treatment of a polymer or oligomeric zinc compound with a suitable complexing agent capable of forming monomeric active species can result in the conversion of aldehydes, ketones, esters and lactones with silanes. It is a very effective catalyst for reduction. According to the present invention, a precursor compound of an oligomer or a polymer, or a dialkyl zinc compound or a diaryl zinc compound can be used after being treated with an appropriate complexing agent to be converted into an active salt or complex. Furthermore, it has been found that a complex or salt of a known monomer which is converted into an active form by the method of the present invention can be used, but its activity has not been known at all. As a precursor compound, actually, the general formula ZnX Two Can be used. In the formula, X means any anion. Preferred anions X are shown below. The active catalyst of the present invention has the general formula ZnX Two L n Can be represented by The catalyst has the general formula ZnX described above. Two Can be obtained in situ in the reaction medium from a zinc compound such as a salt or complex represented by and synthesized separately. General formula ZnX Two And ZnX represented by the formula: Two L n X in the active catalyst represented by is preferably carboxylate, β-diketonate, enolate, amide, silylamide, halide, carbonate and cyanide, and alkyl, cycloalkyl, alkoxy, aryl, aryloxy, alkoxyalkyl, alkoxyaryl, An anion selected from the group consisting of organic groups such as aralkoxy, aralcoyl and alkylaryl groups. Within this group, for example, the formula Zn (RCO) such as acetate, propionate, butyrate, isobutyrate, isovalerate, diethyl acetate, benzoate, 2-ethylhexanoate, stearate or naphthoate Two ) Two A carboxylate of formula Zn (OR 3) such as methoxide, ethoxide, isopropoxide, tert-butoxide, tert-pentoxide or 8-hydroxyquinolinate Two (Where R is C 1 ~ C Two 0, preferably C 1 ~ C Five Substituted or unsubstituted acetylacetonate, zinc β-diketonate such as tropolonate; alkylzinc compounds having 1 to 20, preferably 1 to 5 carbon atoms, arylzinc compounds, alkyl (Alkoxy) zinc compounds, aryl (alkoxy) zinc compounds or derivatives thereof, such as dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, diphenylzinc, methyl (methoxy) or methyl (phenoxy) zinc, or halogenated (alkyl) Derivatives of zinc are advantageously used. Formula ZnX Two L n N in the above is an integer of 1 to 6. Ligands L, which may be the same or different, are selected from the group consisting of amines, polyamines, imines, polyimines, amino alcohols, amine oxides, phosphoramides and amides. The amine is a primary, secondary or tertiary aliphatic, cycloaliphatic or aromatic amine having 2 to 30 carbon atoms. Examples include aniline, triethylamine, tributylamine, N, N-dimethylaniline, morpholine, piperidine, pyridine, picoline, lutidine, 4-terthiobutylpyridine, dimethylaminopyridine, quinoline and N-methylmorpholine. It is not limited to the example. Polyamines have 2 to 6 primary, secondary or tertiary amine groups and consist of 2 to 30 carbon atoms such as ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,2- Butanediamine, 1,3-butanediamine, 1,4-butanediamine, hexamethylenediamine, N, N-dimethylethylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetramethylethylenediamine, N, N-dimethylpropylenediamine, N, N, N'-trimethylethylenediamine, N, N, N ', N'-tetramethyl-1,3-propanediamine, hexamethylenetetramine, diazabicyclononane, sparteine, orthophenanthroline, 2,2'- There are bipyridine and neocuproin. Amino alcohols consist of one or several primary, secondary or tertiary amine groups together with one or several primary, secondary or tertiary alcohol groups, for example ethanolamine, diethanolamine, triethanolamine. There are amines, dimethylaminoethanol, diethylaminoethanol, dimethylaminomethanol, diethylaminomethanol, 2-aminobutanol, ephedrine, prolinol, vallinol, cinchonidine, quinine and quinidine. In the concept of the present invention, as a ligand which belongs to the family of imines or diimines and activates a zinc derivative or a zinc compound, a compound family of the following formulas [I] to [V] (wherein each group R 1 To R 6 Is an alkyl, cycloalkyl, alkoxy, aryl, aryloxy, alkoxyalkyl, alkoxyaryl, aralkoxy, aralkyl, alkylaryl or aralkyl group having 1 to 20 hydrogen atoms or carbon atoms. It is not limited. Other ligands that can activate zinc compounds and zinc derivatives still include amides, e.g., dimethylformamide, dimethylacetamide or N-methyl-pyrrolidone, phosphoramides such as hexamethylphosphortriamide, triphenylphosphine oxide, Phosphine oxides such as tributylphosphine oxide, trioctylphosphine oxide, amine oxides such as pyridine N-oxide, 4-picoline-N-oxide, N-methyl-morpholine N-oxide, sulfoxides such as dimethylsulfoxide or diphenylsulfoxide. There is. The present invention also relates to a monomer of a zinc complex which is activated by the method of the present invention. An advantageous class of compounds are the zinc carboxylate monomers. Zn (O Two CC H Three ) Two (Pyridine) Two This molecular class other than (see J. Am. Chem. Soc. 119, 7030 (1997)) is not described in the chemical literature. Preferred compounds among these complexes include [Zn (benzoate)] Two (Me Two NCH Two CH Two OH) Two ], [Zn (diethyl acetate) Two (2 , 2 ' -Bipyridyl)], [Zn (diethyl acetate) Two (1,2-diaminopropane) Two ] And [Zn (benzoate) Two (TMEDA)] (TMEDA = tetramethylethylenediamine). The synthesis and properties of these compounds are described below. A number of silanes can be used in the method of the present invention. Such silanes are known to those skilled in the art and can be selected depending on their ability to effectively reduce the carbonyl substrate in the method of the present invention. Examples include, but are not limited to, trialkylsilane, dialkylsilane, or trialkoxysilane. More specific examples include dimethylsilane, diethylsilane, trimethoxysilane and triethoxysilane. It is advantageous to use PMHS because of its effectiveness, usefulness and cost. Taking the advantageous case of using PMHS as reducing agent as an example, the method of the present invention is outlined by the following scheme. Catalyst ZnX in mol% per substrate Two L n Is usually 0.1 to 10 mol%, preferably 1 to 5 mol%. PMHS is typically consumed in two molar equivalents per ester or lactone group, one equivalent in the reduction of aldehydes and ketones. In practice, it is advantageous to use a slightly above stoichiometric amount of PMHS, usually in excess of 10 to 40% of stoichiometric. When the silane is used in a quasi-stoichiometric amount, the reduction reaction of the present invention can be carried out, but the conversion amount is reduced as a result. That is, in the present invention, an "effective amount" means that the amount of silane is sufficient to induce reduction of the substrate. The alcohol obtained as reaction product can be obtained by hydrolysis of the formed polysilyl ether. This hydrolysis can be carried out by adding an aqueous or alcoholic solution of a basic agent such as sodium hydroxide, potassium hydroxide, lime, sodium carbonate, potassium carbonate to the reaction mixture. The ratio of base to PMHS used is about 1-2 molar equivalents. After complete hydrolysis, the formation of two phases is generally observed. The desired alcohol is in the organic phase and can be obtained by evaporating the solvent present. The residue obtained may be distilled for further purification. This reduction can be carried out in the absence or presence of a solvent, such as ethers (eg methyl tert-butyl ether, diisopropyl ether, dibutyl ether, tert-amyl methyl ether, tetrahydrofuran or dioxane), aliphatic hydrocarbons (eg heptane) , Petroleum ether, octane, or cyclohexane) or aromatic hydrocarbons (eg, benzene, toluene, xylene or mesitylene) or mixtures thereof. As mentioned above, the reduction of the present invention is applicable to various carbonyl compounds containing unsaturated groups other than carbonyl groups which are not affected by the reduction reaction, such as olefin, acetylene, nitrile or nitro groups. Examples of aldehyde substrates include, but are not limited to, linear or branched butanals, pentanals, heptanals, octanals, decanals, dodecanals. Other unsaturated aldehydes that are selectively reduced to the corresponding unsaturated alcohols include acrolein, methacrolein, prenal, citral, retinal, campholene aldehyde, cinnamaldehyde, hexylcinnamic aldehyde, and formylpinane. And Nopal. Aromatic aldehydes such as benzaldehyde, cuminaldehyde, vanillin, salicylaldehyde or heliotropin are also easily reduced to the corresponding alcohol. As in the present invention, the saturated and unsaturated ketones which are reduced by silane to the corresponding alcohol include hexane-2-one, octane-2-one, nonan-4-one, dodecane-2-one, methyl Vinyl ketone, mesityl oxide, acetophenone, cyclopentanone, cyclodecanone, cyclohexen-1-en-3-one, isophorone, oxophorone, carvone, camphor, β-ionone, geranylacetone and 2-pentylcyclopenten-2-one However, the present invention is not limited to these examples. Saturated and unsaturated esters or lactones reduced by the silane to the corresponding alcohol as in the present invention include acetate, propionate, butyrate, isobutyrate, benzoate, acrylate, crotonate, cinnamate, cis-3-hexenoate, Examples include, but are not limited to, sorbate, salicylate, 10-undecylenate, oleate, linoleate, esters of natural fatty acids, and mixtures thereof. Other examples include, but are not limited to, lactones such as ε-caprolactone, decalactone, dodecalactone, diketene and sclareolide. A notable feature of the catalysts of the present invention is the ability to reduce the natural triglycerides of fatty acids to form vegetable and animal fats. During the reaction of a mixture of triglycerides derived from different fatty acids, saturated and unsaturated natural alcohols can be obtained simultaneously without changing the position and stereochemical structure of the olefin-like double bond. This is particularly significant for olefinic bonds in the cis configuration. In the above scheme (3), the substituent R 1 , R Two And R Three Is a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. If these groups contain one or more specific stereochemical olefin groups (generally cis), the corresponding alcohols obtained after reduction according to the invention have the same stereochemical structure. Thus, fats and oils rich in linoleic acid and / or linolenic acid, such as linseed oil, are converted to a mixture rich in linoleyl alcohol and / or linolenyl alcohol. Conventional methods for hydrogenating vegetable fats, in contrast to the present invention, are usually carried out at high pressure and high temperature. Furthermore, in such conventional hydrogenation, since the methyl ester of each acid obtained by transesterifying an oil or fat with methanol is used, the fatty ester precursor is often used during the transesterification and hydrogenation reactions. The change in the stereochemical structure of is observed. The triglycerides reduced by the method of the present invention include triolein, peanut oil, soybean oil, olive oil, rapeseed oil, sesame oil, grape seed oil, linseed oil, cocoa butter, palm oil, palm kernel oil, cotton oil, copra Oil, coconut oil, and pork, beef, sheep and chicken fats, but are not limited to this example. Other naturally occurring fats and oils that are not triglycerides but are esters of unsaturated fatty acids and monounsaturated alcohols include jojoba oil and whale oil, and the position and steric position of the double bond present in the ester molecule. It can be reduced by the method of the present invention without changing the chemical structure. The reaction temperature can be varied in a wide range of values, usually in the range of -50 to 250C. The temperature chosen depends on the reactivity of the substrate and can be adjusted appropriately without difficulty. More generally, the reaction is carried out in a temperature range from 50 to 110C. The following examples illustrate the invention in more detail. In the examples, the temperature is in degrees Celsius, the yield is mol%, the chemical shift δ of the NMR data is ppm relative to the internal standard tetramethylsilane, and these abbreviations are known to those skilled in the art. Example 1 Complex [Zn (benzoate) Two (Me Two NCH Two CH Two OH) Two This compound was synthesized according to the following description and the example of scheme (4). An exothermic reaction was observed in which 1.8 g (20 mmol) of dimethylaminoethanol was added to a suspension of 3.06 g (10 mmol) of zinc benzoate in 50 ml of dichloromethane, and the zinc benzoate was completely dissolved. After stirring at 20 ° C. for 1 hour, the solvent was evaporated and the solid residue obtained was crystallized from a minimum amount of dichloromethane. 3.9 g (80%) of the desired complex were obtained as white solid crystals, the structure of which was confirmed by X-ray structural analysis from a single crystal. Example 2 Complex [Zn (diethyl acetate) Two Synthesis of (2,2′-bipyridyl)] This compound was synthesized as follows according to scheme (5). 3 g (10 mmol) of zinc diethyl acetate were dissolved in 50 ml of diisopropyl ether. Thereafter, 10 mmol of the ligand 2,2′-bipyridyl were added, and the mixture was then stirred at 20 ° C. A precipitate quickly formed, which was separated by filtration and recrystallized from cyclohexane. The yield was 80%. Example 3 Complex [Zn (benzoate) Two Synthesis of (tetramethylethylenediamine)] This compound was synthesized according to the following description and the outline of scheme (6). The reaction was carried out as described in Example 1, using 1 equivalent of tetramethylethylenediamine instead of 2 equivalents of dimethylaminoethanol. Yield: 85%. Example 4 Complex [Zn (diethyl acetate) Two (1,2-diaminopropane) Two ] Synthesis. This compound was synthesized as follows according to scheme (7). The reaction was carried out as described in Example 2, using 2 equivalents of 1,2-diaminopropane instead of 1 equivalent of 2,2'-bipyridyl. Yield = 75%. Reduction Reaction Example 5 In a 250 ml three-necked flask, 30 g of isopropyl ether and 27.2 g (0.2 mol) of methylbenzoate were then added to the crystalline complex synthesized in Example 2, ie, [Zn (diethyl acetate) Two (2,2'-bipyridyl)]. The mixture was heated (refluxed) to 70 ° C. over 15 minutes and 30 g (0.44 mol) of PMHS was added. The mixture was stirred under reflux for an additional hour until the substrate had completely disappeared (determined by GC analysis). The mixture was cooled to 20 ° C. and, with rapid stirring, 66 g (0.52 mol) of a 45% aqueous solution of KOH, and then stirred for a further hour. Then 100 g of water were added and the mixture was decanted. The aqueous phase containing potassium polymethylsiliconate was decanted and the organic phase was washed with 50 ml of water. The solvent was removed by distillation to obtain 21 g of a crude product. Distillation from the residue yielded 20.5 g of benzyl alcohol with a purity of 98% or more (yield = 95%). Example 6 (Comparative) The reaction was carried out as in Example 5, except that 1.12 g (4 mmol) of the polymer zinc diethyl acetate were used as catalyst. No reaction of the methyl benzoate used was observed even after 4 hours, which indicates that the presence of the appropriate ligand is essential for the depolymerization reaction, and thus for the activation of the diethyl acetate of zinc required for the ester reduction. It is shown that. Examples 7-23 These examples, summarized in Table 1, demonstrate the significant effect of the addition of a bidentate ligand on the catalytic activity of zinc carboxylate in the reduction of methyl benzoate to benzyl alcohol by PMHS. The reaction conditions are listed below the table and are similar to Example 5. From this table, it can be seen that the infrared band of the carboxylate group of the isolated complex υ (CO Two ) as And υ (CO Two ) s Is also known, whereby the depolymerization of the zinc carboxylate precursor can be confirmed before obtaining the catalytic activity. Table 1 Reduction of methyl benzoate to benzyl alcohol. Influence by the nature of the bidentate ligand. Examples 24-30 These examples, summarized in Table 2, demonstrate the significant effect of the addition of a monodentate ligand on the catalytic activity of zinc carboxylate in the reduction of methyl benzoate by PMHS. The reaction was carried out as described above, using 2 mol% of the substrates methylbenzoate and zinc diethylacetate together with 4 mol% of the monodentate ligand. Table 2 Reduction of methyl benzoate by PMHS in the presence of zinc carboxylate complexed with a monodentate ligand. Examples 31-36 These examples show that the addition of the ligands specified so far advantageously affects the catalytic activity of zinc β-diketonates, such as acetylacetonate, used to reduce esters using PMHS. It is shown that. It is known that zinc acetylacetonate has a trimer structure, which is monomeric and octahedral when reacted with a bidentate ligand such as 2,2'-bipyridyl. Table 3 below shows that zinc acetylacetonate itself has low activity in reducing esters with PMHS. By adding one equivalent of a primary or secondary diamine to zinc acetylacetonate, a zinc complex having a catalytic action to completely convert methylbenzoate to the corresponding alcohol can be obtained. Table 3 Reduction of methyl benzoate by PMHS in the presence of zinc acetylacetonate complexed with various ligands. Examples 37-42 These examples demonstrate that the addition of the previously specified ligands advantageously affects the catalytic activity of dialkyl zinc compounds such as diethyl zinc used when reducing esters using PMHS. (Table 4). The dialkylzinc compound is a monomer and has a linear structure in which the angle of C-Zn-C is 180 °, and does not react under the conditions of the present invention. In the presence of a bidentate ligand L such as a tertiary diamine, ZnR Two A monomer complex having a tetrahedral structure represented by L is formed [see O'Brien et al., J Organomet. Chem., 1993, 449, let1993, 461, 5]. Table 4 Reduction of methyl benzoate by PMHS in the presence of diethyl zinc complexed with various ligands. Examples 43-47 These examples show that the addition of the ligands specified so far has an advantageous effect on the catalytic activity of the zinc alkoxide used when reducing esters using PMHS. Table 5 shows that zinc tert-pentoxylate, formed in situ, by adding 2 equivalents of anhydrous zinc chloride 1 equivalent of potassium tert-pentoxide (in toluene solution) is remarkable for the reduction of methylbenzoate by PMHS. It does not show any high activity, but shows that adding a primary, secondary or tertiary diamine results in a highly active catalyst. Table 5 Reduction of methyl benzoate by PMHS in the presence of zinc alkoxides complexed with various ligands. Examples 48-52 The reaction was carried out as described in Example 5, using a mixture containing 2 mol% of zinc diethyl acetate and 2 mol% of dimethylaminoethanol per substrate under reflux of diisopropyl ether. 20 mmol of each ester was used and reduced with 44 mmol of PMHS. When the substrate disappeared, it was hydrolyzed with 60 mmol of KOH (in the form of a 45% aqueous solution of KOH). After decantation and evaporation of the solvent, the resulting alcohol was distilled. As can be seen from the results shown in Table 6, in no case did the stereochemical structure of the starting compound be affected. Table 6 Reduction of various esters by PMHS in the presence of zinc diethyl acetate complexed with dimethylaminoethanol. Examples 53-59 The reaction was carried out as described in Example 5, using a mixture containing 2 mol% of zinc diethyl acetate and 2 mol% of one of the ligands listed in Table 7 per substrate under reflux of diisopropyl ether. It was carried out. 20 mmol of each aldehyde or ketone was used as a substrate, and reduced with 22 mmol of PMHS. When the substrate had completely disappeared, it was hydrolyzed with 60 mmol of KOH (in the form of a 45% aqueous solution of KOH). After decantation and evaporation of the solvent, the resulting alcohol was distilled. The results in Table 7 show that the reduction of the aldehydes and ketones in both reactions proceeded in good yield without changing the stereochemical structure of the starting materials. Table 7 Reduction of various aldehydes and ketones by PM HS in the presence of zinc diethyl acetate complexed with various ligands. Examples 60-62 This reaction was carried out using ZnF as a catalyst. Two And carried out in the same manner as described in Example 5. The results showed that the zinc halide was active in this type of reduction. Table 8 ZnF complexed with various ligands Two Of methyl benzoate with PMHS in the presence of. Example 63 Reduction of Peanut Oil A three-necked 11 flask was charged with 200 ml of toluene, 11 g (0.03 mol) of zinc 2-ethylhexanoate and 5.34 g (0.06 mol) of dimethylaminoethanol. Next, 200 g of peanut oil was added and the mixture was heated under reflux (110 ° C.). Over a period of 1 hour, 200 g (0.5 mol) of PMHS were added and the mixture was refluxed for a further 2 hours. Thereafter, a sample hydrolyzed with a 30% methanol solution of KOH was subjected to GC analysis. As a result, the amount of alcohol in the reaction mixture was constant. The mixture was then poured into 450 g of a 30% solution of KOH in methanol and kept at 50 ° C. for a further hour. Then 300 g of water were added and the mixture was decanted. The solvent was then evaporated from the organic phase and the residue was distilled at 200-250 ° C./1 hPa, giving 100 g of a mixture containing 14% 1-hexadecanol, 55% oleyl alcohol and 17% linoleyl alcohol. Example 64 Reduction of ethyl sorbate Zn (2-ethylhexanoate) in an 11 three-necked flask equipped with a reflux condenser, internal thermometer, syringe pump and magnetic stirrer Two 13.3 g (4 mol% per substrate), 4 g (4 mol%) of dimethylaminoethanol and 10 ml of toluene were added and heated to 80 ° C. Then 210.1 g (1.5 mol) of ethyl sorbate, 0.42 g of BHT (2,4-di-tert-butyl-p-cresol) and toluene (ca 200 ml) were added, and the solution was refluxed. 213 g (equivalent to 2.1 equivalents) of PMHS were added over 90 minutes and the reaction mixture was heated at reflux for a further 30 minutes. The mixture was poured onto 630 g of a 30% aqueous solution of NaOH until complete hydrolysis, the organic phase was decanted and washed with water. The crude product was distilled on a vigreux type column (10 hPa) to give 120.7 g (83.4%) of hexa-2,4-dien-1-ol. Example 65 Reduction of jojoba oil 50 g of jojoba oil, Zn (2-ethylhexanoate) in a 250 ml three-necked flask equipped with a reflux condenser, an internal thermometer, a syringe pump and a magnetic stirrer Two 0.2 g (corresponding to about 4 mol% per ester group), 0.06 g (about 4 mol%) of dimethylaminoethanol and 50 ml of toluene were added. The mixture was heated at reflux and 6.5 g (0.1 mol, about 2.2 equiv.) Of PMHS was added over 45 minutes. Reflux was continued for another 30 minutes and the reaction mixture was poured into 50 g of a 30% aqueous solution of NaOH. After complete hydrolysis, the organic phase was decanted and washed with water. The crude product thus obtained was distilled in a bulb-to-bulb apparatus at 250 ° / 1 hPa, 6.4% of (Z) -9-octadecane-1-ol, (Z) -9 A product 48.4 containing 59.3% of icosen-1-ol, 26.8% of (Z) -9-docosen-1-ol and 3.9% of (Z) -9-tetracosen-1-ol. g (95%).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI テーマコート゛(参考) C07C 33/02 C07C 33/02 53/126 53/126 63/06 63/06 211/09 211/09 215/08 215/08 C07D 213/16 C07D 213/16 213/22 213/22 295/02 295/02 Z // C07B 61/00 300 C07B 61/00 300 C07F 3/06 C07F 3/06 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C07C 33/02 C07C 33/02 53/126 53/126 63/06 63/06 211/09 211/09 215 / 08 215/08 C07D 213/16 C07D 213/16 213/22 213/22 295/02 295/02 Z // C07B 61/00 300 C07B 61/00 300 C07F 3/06 C07F 3/06
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Cited By (6)
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JP2002516828A (en) * | 1998-06-01 | 2002-06-11 | アンソニー・ジェイ・バービスカー | Topical transdermal treatment |
JP2006241100A (en) * | 2005-03-04 | 2006-09-14 | Tokyo Univ Of Science | Method for producing optically active alcohol |
JP2010222335A (en) * | 2009-02-27 | 2010-10-07 | Nagoya Univ | Method for producing optically active alcohol |
JP2016501954A (en) * | 2012-12-20 | 2016-01-21 | ブルースター・シリコーンズ・フランス・エスアエス | Organopolysiloxane composition suitable for vulcanization to elastomer at room temperature and novel organopolysiloxane polycondensation catalyst |
JP2016508083A (en) * | 2012-12-20 | 2016-03-17 | ブルースター・シリコーンズ・フランス・エスアエス | Articles with antifouling properties intended for underwater applications, especially marine applications |
JP2016509546A (en) * | 2012-12-20 | 2016-03-31 | ブルースター・シリコーンズ・フランス・エスアエス | Articles with antifouling properties intended for underwater applications, especially marine applications |
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CA2298533A1 (en) * | 1997-09-09 | 1999-03-18 | Firmenich S.A. | Reduction enantioselective de cetones avec un systeme agent silanique/compose metallique/ligand chiral |
DE69907589T2 (en) * | 1998-04-01 | 2004-03-25 | Firmenich S.A. | REDUCTION OF CARBONYL COMPOUNDS WITH A SILANE DERIVATIVE IN THE PRESENCE OF A ZINC CATALYST |
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US3061424A (en) | 1957-02-06 | 1962-10-30 | Wacker Chemie Gmbh | Method of reducing organometallic compounds |
GB8902228D0 (en) * | 1989-02-01 | 1989-03-22 | Ici Plc | Carbodiimide-isocyanurate rigid foams |
US5227538A (en) * | 1990-11-21 | 1993-07-13 | Massachusetts Institute Of Technology | Catalytic asymmetric reduction of ketones using metal catalysts |
US5220020A (en) | 1990-11-21 | 1993-06-15 | Massachusetts Institute Of Technology | Catalytic reduction of organic carbonyls using metal catalysts |
US5449736A (en) * | 1993-07-16 | 1995-09-12 | Research Foundation Of The State Of New York | Water soluble phosphorylated polysiloxanes |
ES2137542T3 (en) * | 1994-10-19 | 1999-12-16 | Firmenich & Cie | PROCEDURE FOR THE PREPARATION OF ALCOHOLS. |
CA2298533A1 (en) * | 1997-09-09 | 1999-03-18 | Firmenich S.A. | Reduction enantioselective de cetones avec un systeme agent silanique/compose metallique/ligand chiral |
DE69907589T2 (en) * | 1998-04-01 | 2004-03-25 | Firmenich S.A. | REDUCTION OF CARBONYL COMPOUNDS WITH A SILANE DERIVATIVE IN THE PRESENCE OF A ZINC CATALYST |
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- 1999-02-25 DE DE69907589T patent/DE69907589T2/en not_active Expired - Lifetime
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002516828A (en) * | 1998-06-01 | 2002-06-11 | アンソニー・ジェイ・バービスカー | Topical transdermal treatment |
JP2006241100A (en) * | 2005-03-04 | 2006-09-14 | Tokyo Univ Of Science | Method for producing optically active alcohol |
JP2010222335A (en) * | 2009-02-27 | 2010-10-07 | Nagoya Univ | Method for producing optically active alcohol |
JP2016501954A (en) * | 2012-12-20 | 2016-01-21 | ブルースター・シリコーンズ・フランス・エスアエス | Organopolysiloxane composition suitable for vulcanization to elastomer at room temperature and novel organopolysiloxane polycondensation catalyst |
JP2016508083A (en) * | 2012-12-20 | 2016-03-17 | ブルースター・シリコーンズ・フランス・エスアエス | Articles with antifouling properties intended for underwater applications, especially marine applications |
JP2016509546A (en) * | 2012-12-20 | 2016-03-31 | ブルースター・シリコーンズ・フランス・エスアエス | Articles with antifouling properties intended for underwater applications, especially marine applications |
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US6245952B1 (en) | 2001-06-12 |
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US20010034464A1 (en) | 2001-10-25 |
US6770588B2 (en) | 2004-08-03 |
ES2198886T3 (en) | 2004-02-01 |
DE69907589T2 (en) | 2004-03-25 |
CN1208295C (en) | 2005-06-29 |
US20030171210A1 (en) | 2003-09-11 |
US6533960B2 (en) | 2003-03-18 |
ATE239685T1 (en) | 2003-05-15 |
JP4169801B2 (en) | 2008-10-22 |
EP0986527A1 (en) | 2000-03-22 |
DE69907589D1 (en) | 2003-06-12 |
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